Fluorophenylmercaptomethyl esters of pentavalent thiophosphorus acids



United States Patent Bayer Aktiengesellschaft, Lever- The present invention relates to and has as its objects new and useful insecticidal phosphorus containing derivatives of fluorophenylthiomethyl ether, and processes for their production. Generally the new compounds according to this invention may be [illustrated by the following a, formula F Rn wherein R stands for an alkyl, alkenyl, aryl, alkoxy or amino group and R stands for an alkyl or amino group. Some fluoropnenyl mereaptomethyl-dithiophosphoric acid esters are already known from British-patent specification No. 772,213. According to the data of the aforesaid British specification these; compounds possess good insecticidal properties.

The object of the present of a constitution similar to invention is a class of esters that of the compounds de- 3,081,328 Patented Mar. 12, 1963 2 ride with the potassium salt of dimethyl-dithiophosphinic acid:

The new compounds are excellent pest control agents which are distinguished by an insecticidal and acaricidal action. The new compounds are applied in-a manner known in principle, namelyin combination with suitable solid or liquid extenders or diluents. Solid extenders are talc, chalk, bentonite, kieselguhror the like, and the preferred liquid diluent is water. If the compounds are not scribed in the above mentioned British specification and a deriving from 'amino-thiolphosphoric acids, amino-dithiophosphoric acids, thiolphosph-onic acids, dithiophosphonic acids, thiolphosphinic acids or di-thiophosphinic'acids, i.e. those compounds of the above shown formula in which no more than one of the groups R, and R can be an alkoxy group. j .1

-More specifically said the compounds of the present invention can be such compounds of the above shown formula in which the alkyl group is a lower alkyl or alkenyl group such as methyl, ethyl, propyl, butyl, arnyl, hexyl, cyclohexyl, propanyl, butenyl, pentanyl, octanyl group and the like. If R, is. an aryl group, this group especially may be a phenyl group or a substituted phenyl group substituted by such groups as a chlorine atom, a

bromine atom, a methyl group, an ethyl group, 2. nitro group, an alkoxy like. R 'if an alkoxy group preferably is a lower alkoxy group containing up to 4 carbon atoms in the alkyl radical, if an amino group this group also may be substituted by l or 2 lower alkyl radicals such as methyl, ethyl, propyl, or butyl groups, or the amino group may be the radical of a cyclic amine such as pyrrolidine, piperidine, piperazine, morpholine and the like. Also R may stand for the same alkyl or amino groups as defined above. The fluoro atom in the benzene nucleus may stand in either 0-, mor p-position and the phenyl nucleus additionally may contain substituents such as those mentioned above in case of R being aryl.

The new compounds according to the invention are obtained in a manner known in principle by the reaction of fluoro-phenyl-mercaptomethyl halides with the corresponding salts of aminothiol or amino-dithio-phosphoric acids, thiolor dithio-phosphonic acids or thiolor dithiophosphinic acids. The reaction may be exemplified by the conversion of pwfluorophenyl-mercaptomethyl chlogroup, an alkylmercapto group and the water-soluble, the use of a solvent or a suitable commercial emulsifier is advisable or necessary.

As an example for the special utility of the inventive compounds the compounds of the following formulae (I) r o 0on1,

. F--,SCHz-Si a. i i 002E; have been tested against spider'mites and aphids (in case of compounds I and II) and against spider mites, aphids and larvae of the type Aedes aegypti (in case of compounds I, II and III). Aqueous solutions or these compounds have been prepared by mixing the active ingredient with the same amount of dimethyl formamide as an auxiliary solvent adding thereto 20% by weight referred to active ingredient of a commercial emulsifier consisting of a benzyl hydroxy polyglycol ether containing about 10 to 15 glycol residues, and diluting at last this premixture with water to the desired concentrations indicated in the following paragraphs:

The tests have been carried out as follows:

(a) Against' spider mites-Bean plants (Phaseolus vulgaris) of about 15 inches height have been sprayed drip wet with solutions prepared as indicated above. The bean plants have been infested heavily with the two-spotted spider (species Tetranychus telarius). Evaluation has been carried out after Q4 hours, 48 hours and 8 days. The following results have been obtained:

Aqueous concentration (in Killing rate Compound percent active (in percent) ingredient] water) (b) Against aphids (Doralis fabae). Heavily infested bean plants (Vicia faba) have been sprayed drip wet with solutions as prepared above. The effect has been determined after 24 hours by counting the dead pests either on the surface of the soil or still remaining on the plants. The following results have been obtained:

Aqueous concentration (in Killing rate Compound percent active (in percent) ingredient] water) Against larvae of the type Aedes aegypti.-About 20 larvae were brought into diluted aqueous emulsions prepared as described above. Counting of the dead pests occurred after 24 hours. The following results have been obtained:

Aqueous con- The following examples are given for the purpose of illustrating the invention:

Example 1 65 grams (0.4 mol) of the sodium salt of amino-ethylthiolphosphoric acid and 44 g. (0.25 mol) of 4-fluoro phenyl-mercapto-methyl chloride are warmed to 60-70 C. for 2-3 hours in 150 cc. of acetonitrile. After cooling, the sodium chloride is filtered OE With suction and the solvent removed under vacuum. The remaining oil is taken up with benzene, washed with water, dried and freed from the solvent. The oil thus obtained which cannot be distilled, is light brown and somewhat viscous. Yield: 65 grams corresponding to 92.6% of the theoretical.

By the same way as described above there are prepared the following compounds which showed also good insecticidal activities:

47 grams (0.3 mol) of the ammonium salt of diethylthiolphosphinic acid and 44 grams (0.25 mol) of 4-fluorophenyl-mercaptomethyl chloride in 150 cc. of n-propyl alcohol are warmed to 60-70 C. for two hours. The product is then diluted with Water. The precipitated oil is taken up with benzene, washed with water and sodium bicarbonate, dried and freed from the solvent. The remaining oil distils after slight first runnings at C./0.01 mm. Hg as a pale yellow oil. Yield: 40 grams corresponding to 57.5% of the theoretical.

:By the same way as described above there are prepared the following compounds which showed also good insecticidal activities:

O CQH5 OzHa S C 1H5 C2115 Example 3 49 grams (0.3 mol) of the potassium salt of methylthionothiolphosphonic acid ethyl ester and 44 grams 0.25 mol) of 4-fluorophenyl-mercaptomethyl chloride in cc. of acetone are stirred overnight at room temperature and warmed in the morning to 50-60" C. for an hour. After cooling, the solution is poured into water and the oil is extracted with benzene. After washing with water and sodium bicarbonate, the product is dried over sodium sulfate. The solvent is distilled off and the remaining oil distilled under high vacuum. The ester boils at 108-109 C. as a pale yellow water-insoluble oil. Yield: 65 grams corresponding to 89.2% of the theoretical. LD on rats per os: 10 rug/kg.

By the same way as described above there are prepared the following compounds which showed also good insecticidal activities:

s OH=OHOOH1 S CH=U (CH3):

II/ F s-on S-P 0 0:11 Example 4 By the same way as described above there are prepared the following compounds which showed also good insecticidal activities:

The insecticidal activities of the inventive compounds are to be seen from the following table:

Aqueous Killing Cmpd. Test animal c0110., rate,

percent percent Aphids '0. 1 100 Ex. 1-- {Spider mites 0.01 100 3 1 Syst.actin 0.1 100 Aphids 0.01 100 LD Ex. 2-. Spider mites 0.01 100 mg'lkg Syst.aetion, ovicidal action.-- 0.1 180 v cmkrmehes "{3201 108 LD Ex. 3-- Mose. larvae 0.00001 100 g Spider mites, ovicidal act n 0.0001 60 Aphids 0.001 100 E 4 {Spider mites 0.01 50 }LD 5, 500 Ovicidal action, syst. aeti0n 0.1 100 rug/kg.

We claim: 1. A compound of the following formula in which R and R stand for a member selected from the group consisting of lower alkyl and alkenyl groups up to 4 carbon atoms, phenyl groups, lower alkoxy groups up to 4 carbon atoms, amino groups and lower alkyl-substituted amino groups, only one of R and R being a lower alkoxy group, and X stands for a member selected from the group consisting of oxygen and sulfur.

2. A compound of the following formula X OR:

in which R stands for a lower alkyl radical up to 4 carbon atoms, R; and R stand for a member selected from the group consisting of hydrogen and lower alkyl radicals up to 4 carbon atoms, and X stands for a member selected from the group consisting of oxygen and sulfur.

3. A compound of the following formula in which R stands for a lower alkyl radical up to 4 carbon atoms, R stands for a member selected from the group consisting of lower alkyl and alkenyl groups up to 4 carbon atoms and phenyl groups, and X stands for a member selected from the group consisting of oxygen and sulfur.

4. A compound of the following formula in which R11 and R stand for a member selected from the group consisting of lower alkyl and alkenyl groups up to 4 carbon atoms and phenyl groups, and X stands for a member selected from the group consisting of oxygen and sulfur.

-5. The compound of the following formula No references cited. 

1. A COMPOUND OF THE FOLLOWING FORMULA 